CN115806701A - High-hardness wear-resistant durable hydrogenated nitrile rubber compound and preparation method thereof - Google Patents
High-hardness wear-resistant durable hydrogenated nitrile rubber compound and preparation method thereof Download PDFInfo
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- CN115806701A CN115806701A CN202211432807.3A CN202211432807A CN115806701A CN 115806701 A CN115806701 A CN 115806701A CN 202211432807 A CN202211432807 A CN 202211432807A CN 115806701 A CN115806701 A CN 115806701A
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- nitrile rubber
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- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 61
- 150000001875 compounds Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 241000872198 Serjania polyphylla Species 0.000 claims abstract description 15
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008117 stearic acid Substances 0.000 claims abstract description 15
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 9
- 150000002978 peroxides Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 7
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 34
- 238000005299 abrasion Methods 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- AXTADRUCVAUCRS-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrole-2,5-dione Chemical compound OCCN1C(=O)C=CC1=O AXTADRUCVAUCRS-UHFFFAOYSA-N 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 8
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- HYTJADYUOGDVRL-UHFFFAOYSA-N n-phenyl-n-(2-phenylpropan-2-yl)aniline Chemical compound C=1C=CC=CC=1C(C)(C)N(C=1C=CC=CC=1)C1=CC=CC=C1 HYTJADYUOGDVRL-UHFFFAOYSA-N 0.000 claims description 8
- -1 saturated fatty acid esters Chemical class 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims description 4
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 75
- 239000005060 rubber Substances 0.000 abstract description 75
- 238000013016 damping Methods 0.000 abstract description 7
- 230000006835 compression Effects 0.000 abstract description 4
- 238000007906 compression Methods 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000007599 discharging Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007799 cork Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CXUGZITZWVNSNK-UHFFFAOYSA-N 1-tert-butylperoxy-4-(2-tert-butylperoxypropan-2-yl)benzene Chemical compound C(C)(C)(C)OOC(C)(C)C1=CC=C(C=C1)OOC(C)(C)C CXUGZITZWVNSNK-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a high-hardness wear-resistant durable hydrogenated nitrile rubber compound and a preparation method thereof, wherein the compound comprises the following raw materials in parts by weight: 80-100 parts of hydrogenated nitrile rubber, 4-7 parts of zinc oxide, 0.5-2 parts of stearic acid, 30-60 parts of carbon black, 0-15 parts of white carbon black, 0-20 parts of filler, 1-3 parts of aniline anti-aging agent, 0-15 parts of processing aid and 3-6 parts of peroxide vulcanizing agent; the white carbon black is the white carbon black with the surface grafted with maleimide. The high-hardness wear-resistant durable hydrogenated nitrile butadiene rubber compound and the preparation method thereof have the advantages that the compound has excellent performances such as hardness, tensile strength at break, elongation at break, compression resilience, wear resistance and the like, and can effectively meet the requirement of durability of the compound for a rubber damping block.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a high-hardness wear-resistant durable hydrogenated nitrile rubber compound and a preparation method thereof.
Background
With the rapid development of the field of electric automobiles in recent years, the functions of the electric automobiles are more and more abundant. The range-extended electric automobile is one of electric automobiles, and an engine and a generator are mechanically connected to form a range extender which is only used for generating electricity. The existing coupling for the range extender is complex in structure and complex in assembly, can occupy a large amount of space of a vehicle body and obstruct the installation of other parts, so that the internal space of the vehicle is reduced, and various parts are inconvenient to arrange. The driving disc and the driven disc are connected through the damping disc, the arrangement of the damping disc can limit the relative positions of the driving disc and the driven disc, the axial deviation of the driving disc and the driven disc is reduced, the torque transmission efficiency is guaranteed, and noise is avoided; in the axial direction, the three are mutually inserted and connected into a whole, so that the axial size of the coupler is reduced, the space occupied by the coupler can be reduced, the internal space of a vehicle body is saved, the space is provided for the installation of other equipment, the axial deviation of the range extender in the process of transmitting torque can be reduced, and the noise is avoided. Therefore, the damping disc is an important component of a new extended-range electric automobile, and the durability of the damping disc determines the service life of the electric automobile.
Considering that one of the most important parts affecting the durability of the damper disc is the rubber damper block in the damper disc, it is important to produce a high-quality rubber damper block. The rubber damper block is usually produced by vulcanizing rubber compound, but the existing rubber damper block made by vulcanizing natural rubber or chloroprene rubber is easy to lose or crack prematurely and lose and become sticky due to too large torsion angle when being impacted, so that the requirement on the durability of the rubber damper block cannot be met.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-hardness wear-resistant durable hydrogenated nitrile rubber compound and a preparation method thereof, wherein the compound has excellent performances such as hardness, breaking strength, breaking elongation, pressure-variable resilience, wear resistance and the like, and can effectively meet the requirement of the compound on durability of a rubber damping block.
The invention provides a high-hardness wear-resistant durable hydrogenated nitrile rubber compound which comprises the following raw materials in parts by weight:
80-100 parts of hydrogenated nitrile rubber, 4-7 parts of zinc oxide, 0.5-2 parts of stearic acid, 30-60 parts of carbon black, 0-15 parts of white carbon black, 0-20 parts of filler, 1-3 parts of aniline anti-aging agent, 0-15 parts of processing aid and 3-6 parts of peroxide vulcanizing agent;
the white carbon black is the white carbon black with the surface grafted with maleimide.
According to the invention, the hydrogenated nitrile rubber is adopted, and the carbon black and the white carbon black are reasonably compounded, so that the obtained rubber compound not only has higher hardness and wear resistance, but also has obviously improved flexibility; meanwhile, a peroxide vulcanization system is compounded, so that the requirements of high resilience and high wear resistance of the obtained rubber compound are further met; further, the acrylonitrile in the hydrogenated nitrile rubber also provides excellent oil resistance to the rubber compound.
Preferably, the acrylonitrile content of the hydrogenated nitrile rubber is more than 25%, the Mooney viscosity ML1+4 at 100 ℃ is 50-90, and the iodine value is 10-35mg/100mg.
Hydrogenated nitrile rubber (HNBR) is a highly saturated elastomer obtained by carrying out special hydrotreatment on nitrile rubber, and has good oil resistance and higher compression set resistance; in the invention, the content of acrylonitrile in the hydrogenated nitrile-butadiene rubber is limited to be more than 25%, the Mooney viscosity ML1+4 at 100 ℃ is 50-90, and the iodine value is 10-35mg/100mg, so that the hydrogenated nitrile-butadiene rubber has the advantages of high strength, high tearing performance, excellent wear resistance and the like.
Preferably, the carbon black is at least one of carbon black N330, carbon black N375, or carbon black N339.
Preferably, the white carbon black with the maleimide grafted on the surface is obtained by heating white carbon black and N- (2-hydroxyethyl) maleimide to 50-70 ℃ under the condition of a dibutyltin dilaurate catalyst and reacting for 3-5 h;
preferably, the mass ratio of the white carbon black to the N- (2-hydroxyethyl) maleimide is 10-15.
Although the white carbon black has better extensibility and tearability, the dispersibility is not very good, in the invention, silicon hydroxyl on the surface of the white carbon black and hydroxyl of N- (2-hydroxyethyl) maleimide are condensed to generate an ether compound, so that maleimide is grafted on the surface of the white carbon black; in the white carbon black with the maleimide grafted on the surface, on one hand, double bonds existing in the maleimide can generate a crosslinking reaction with residual unsaturated bonds in hydrogenated nitrile rubber, so that the crosslinking degree of the obtained rubber compound is increased, the mechanical property is enhanced, on the other hand, the defect of poor dispersibility of the white carbon black in the rubber compound matrix is overcome, and the dispersibility and the affinity of the white carbon black in the rubber compound matrix are enhanced, so that a more excellent reinforcing effect is shown, and the mechanical properties of high hardness and high resilience are obtained; in addition, the amide group contained in the maleimide structure can further improve the abrasion resistance of the resulting rubber compound.
In the invention, the structure of the white carbon black with the maleimide grafted on the surface is shown as follows:
preferably, the filler is a silicate;
preferably, the silicate is at least one of magnesium aluminum hydrotalcite or calcined kaolin.
Preferably, the aniline antioxidant is at least one of 4,4' -bis (phenylisopropyl) diphenylamine, N-isopropyl-N ' -phenyl-p-phenylenediamine or N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine.
Preferably, the processing aid comprises a saturated fatty acid ester and/or erucamide.
Preferably, the peroxide curing agent is at least one of 1, 4-bis-tert-butylperoxyisopropyl benzene, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, dicumyl peroxide, or 1, 3-bis (2-tert-butylperoxyisopropyl) benzene.
The invention also provides a preparation method of the high-hardness wear-resistant durable hydrogenated nitrile rubber compound, which comprises the following steps: adding hydrogenated nitrile rubber, zinc oxide, stearic acid, carbon black, white carbon black, a filler, an aniline anti-aging agent and a processing aid into an internal mixer, mixing uniformly, adding a peroxide vulcanizing agent, mixing uniformly, and finally vulcanizing to obtain a finished product, namely the high-hardness wear-resistant durable hydrogenated nitrile rubber compound.
Preferably, the vulcanization temperature is 155-165 ℃ and the vulcanization time is 20-60min.
The invention adopts the hydrogenated nitrile rubber as the main material, so that the rubber compound has good ozone resistance and high temperature resistance; the carbon black and the white carbon black with the maleimide grafted on the surface are compounded to be used as a reinforcing filler, so that the mixed rubber can keep higher tensile strength and low compression permanent deformation; the aniline anti-aging agent is adopted to improve the ozone resistance and the heat resistance of the rubber material; peroxide is used as a vulcanization system, so that the compression permanent deformation performance and the high-low temperature elasticity of the rubber material are improved. Compared with the prior art, the rubber shock-absorbing block disclosed by the invention better realizes high resilience and high wear resistance of the rubber material and meets the requirement on durability of the rubber shock-absorbing block.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A high-hardness wear-resistant durable hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:
90 parts of hydrogenated nitrile rubber, 6 parts of zinc oxide, 1 part of stearic acid, 33045 parts of carbon black N, 8 parts of white carbon black, 10 parts of calcined kaolin, 2 parts of 4,4' -bis (phenylisopropyl) diphenylamine, 7 parts of erucamide and 4 parts of 1, 4-di-tert-butylperoxyisopropyl benzene;
wherein the acrylonitrile content of the hydrogenated nitrile-butadiene rubber is 35.5 percent, the Mooney viscosity ML1+4 at 100 ℃ is 71, and the iodine value is 22mg/100mg; the white carbon black is white carbon black with maleimide grafted on the surface, and the preparation method comprises the following steps: adding white carbon black and N- (2-hydroxyethyl) maleimide into ethanol according to the mass ratio of 12, uniformly stirring, adding 1wt% of dibutyltin dilaurate of white carbon black, heating to 60 ℃, stirring for 4 hours, and evaporating to remove ethanol to obtain the white carbon black with the maleimide grafted on the surface.
The high-hardness wear-resistant durable hydrogenated nitrile rubber compound is prepared by the following method:
(1) First-stage mixing: adding hydrogenated nitrile rubber into an internal mixer, mixing for 45 seconds, then adding zinc oxide, stearic acid, erucamide, 4' -bis (phenylisopropyl) diphenylamine, carbon black N330, white carbon black and calcined kaolin, mixing for 50 seconds, lifting and turning rubber, pressing down a top plug, mixing to 140 ℃, discharging rubber, wherein the top plug is lifted once at 120 ℃ and 135 ℃ for 20 seconds respectively, and obtaining a section of rubber;
(2) And (3) second-stage mixing: standing the first-stage rubber for 20 hours, adding 1, 4-di-tert-butylperoxyisopropyl benzene, mixing to 110 ℃, and discharging rubber to obtain final rubber;
(3) And (3) vulcanization: and (4) after the final rubber compound is molded, sending the final rubber compound into a vulcanizing machine, and vulcanizing for 40 minutes at the temperature of 160 +/-5 ℃ to obtain the rubber compound.
Example 2
A high-hardness wear-resistant durable hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:
80 parts of hydrogenated nitrile rubber, 7 parts of zinc oxide, 0.5 part of stearic acid, 30 parts of carbon black N33030, 530 parts of carbon black N37530, 20 parts of magnesium aluminum hydrotalcite, 1 part of N-isopropyl-N' -phenyl-p-phenylenediamine, 7 parts of WB222 saturated fatty acid ester, 8 parts of erucamide and 3 parts of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane;
wherein the hydrogenated nitrile rubber has an acrylonitrile content of 35.5%, a Mooney viscosity ML1+4 at 100 ℃ of 71 and an iodine value of 22mg/100mg.
The high-hardness wear-resistant durable hydrogenated nitrile rubber compound is prepared by the following method:
(1) First-stage mixing: adding hydrogenated nitrile rubber into an internal mixer, mixing for 30 seconds, then adding zinc oxide, stearic acid, saturated fatty acid ester, erucamide, N-isopropyl-N' -phenyl p-phenylenediamine, carbon black N330, carbon black N375 and magnesium aluminum hydrotalcite, mixing for 60 seconds, lifting the cork and turning over the rubber, pressing down the cork, mixing to 140 ℃, and discharging the rubber, wherein the cork is lifted up once at 120 ℃ and 135 ℃ respectively for 10 seconds to obtain a section of rubber;
(2) And (3) second-stage mixing: standing the first-stage rubber for 24 hours, adding 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, mixing to 100 ℃, and discharging rubber to obtain final rubber;
(3) And (3) vulcanizing: and (4) after the final rubber compound is molded, sending the final rubber compound into a vulcanizing machine, and vulcanizing for 60 minutes at the temperature of 160 +/-5 ℃ to obtain the rubber compound.
Example 3
A high-hardness wear-resistant durable hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:
100 parts of hydrogenated nitrile rubber, 4 parts of zinc oxide, 2 parts of stearic acid, 3 parts of carbon black N33930, 15 parts of white carbon black, 3 parts of N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine and 6 parts of dicumyl peroxide;
wherein the acrylonitrile content of the hydrogenated nitrile rubber is 35.5%, the Mooney viscosity ML1+4 at 100 ℃ is 71, and the iodine value is 22mg/100mg; the white carbon black is white carbon black with maleimide grafted on the surface, and the preparation method comprises the following steps: adding white carbon black and N- (2-hydroxyethyl) maleimide into ethanol according to the mass ratio of 12, uniformly stirring, adding 1wt% of dibutyltin dilaurate of white carbon black, heating to 60 ℃, stirring for 4 hours, and evaporating to remove ethanol to obtain the white carbon black with the maleimide grafted on the surface.
The high-hardness wear-resistant durable hydrogenated nitrile rubber compound is prepared by the following method:
(1) First-stage mixing: adding hydrogenated nitrile rubber into an internal mixer, mixing for 60 seconds, then adding zinc oxide, stearic acid, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, carbon black N339 and white carbon black filler, mixing for 30 seconds, lifting and turning rubber, pressing down a top plug, mixing to 140 ℃, and discharging rubber, wherein the top plug is lifted once at 120 ℃ and 135 ℃ for 30 seconds respectively to obtain a section of rubber;
(2) And (2) two-stage mixing: standing the first-stage rubber for 16 hours, adding dicumyl peroxide, mixing to 120 ℃, and discharging rubber to obtain final rubber;
(3) And (3) vulcanization: and (4) after the final rubber compound is molded, sending the final rubber compound into a vulcanizing machine, and vulcanizing for 20 minutes at the temperature of 160 +/-5 ℃ to obtain the rubber compound.
Example 4
A high-hardness wear-resistant durable hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:
90 parts of hydrogenated nitrile rubber, 5 parts of zinc oxide, 1.5 parts of stearic acid, carbon black N33040 parts, 10 parts of white carbon black, 5 parts of calcined kaolin, 2 parts of 4,4' -bis (phenylisopropyl) diphenylamine, 6 parts of WB222 saturated fatty acid ester and 5 parts of 1, 4-di-tert-butylperoxyisopropyl benzene;
wherein the acrylonitrile content of the hydrogenated nitrile-butadiene rubber is 35.5 percent, the Mooney viscosity ML1+4 at 100 ℃ is 71, and the iodine value is 22mg/100mg; the white carbon black is white carbon black with maleimide grafted on the surface, and the preparation method comprises the following steps: adding white carbon black and N- (2-hydroxyethyl) maleimide into ethanol according to the mass ratio of 15 to 1, uniformly stirring, adding 1wt% of dibutyltin dilaurate of the white carbon black, heating to 60 ℃, stirring for 4 hours, and evaporating to remove ethanol to obtain the white carbon black with the maleimide grafted on the surface.
The high-hardness wear-resistant durable hydrogenated nitrile rubber compound is prepared by the following method:
(1) First-stage mixing: adding hydrogenated nitrile rubber into an internal mixer, mixing for 50 seconds, then adding zinc oxide, stearic acid, saturated fatty acid ester, 4' -bis (phenylisopropyl) diphenylamine, carbon black N330, white carbon black and calcined kaolin, mixing for 40 seconds, lifting the cork and turning the rubber, pressing down the upper cork, mixing to 140 ℃, discharging the rubber, wherein the cork is lifted up once at 120 ℃ and 135 ℃ respectively for 20 seconds to obtain a section of rubber;
(2) And (3) second-stage mixing: standing the first-stage rubber for 20 hours, adding 1, 4-di-tert-butylperoxyisopropyl benzene, mixing to 120 ℃, and discharging rubber to obtain final rubber;
(3) And (3) vulcanization: and (3) after the final rubber compound is formed, feeding the final rubber compound into a vulcanizing machine, and vulcanizing for 30 minutes at 160 +/-5 ℃ to obtain the rubber compound.
Comparative example 1
A high-hardness wear-resistant durable hydrogenated nitrile rubber compound comprises the following raw materials in parts by weight:
90 parts of hydrogenated nitrile rubber, 6 parts of zinc oxide, 1 part of stearic acid, 33045 parts of carbon black N, 8 parts of white carbon black, 10 parts of calcined kaolin, 2 parts of 4,4' -bis (phenylisopropyl) diphenylamine, 7 parts of erucamide and 4 parts of 1, 4-di-tert-butylperoxyisopropyl benzene;
wherein the acrylonitrile content of the hydrogenated nitrile rubber is 35.5%, the Mooney viscosity ML1+4 at 100 ℃ is 71, and the iodine value is 22mg/100mg.
The high-hardness wear-resistant durable hydrogenated nitrile rubber compound is prepared by the following method:
(1) First-stage mixing: adding hydrogenated nitrile rubber into an internal mixer, mixing for 45 seconds, then adding zinc oxide, stearic acid, erucamide, 4' -bis (phenylisopropyl) diphenylamine, carbon black N330, white carbon black and calcined kaolin, mixing for 50 seconds, lifting and turning rubber, pressing down a top plug, mixing to 140 ℃, discharging rubber, wherein the top plug is lifted once at 120 ℃ and 135 ℃ for 20 seconds respectively, and obtaining a section of rubber;
(2) And (3) second-stage mixing: standing the first-stage rubber for 20 hours, adding 1, 4-di-tert-butylperoxyisopropyl benzene, mixing to 110 ℃, and discharging rubber to obtain final rubber;
(3) And (3) vulcanization: and (4) after the final rubber compound is molded, sending the final rubber compound into a vulcanizing machine, and vulcanizing for 40 minutes at the temperature of 160 +/-5 ℃ to obtain the rubber compound.
The rubber mixtures obtained in the examples and the comparative examples were subjected to the basic physical and chemical properties test, and the test items are shown in the following Table 1.
TABLE 1 results of tests on basic physical and chemical properties of rubber mixtures obtained in examples and comparative examples
As can be seen from the above table, the performance of the rubber mixtures of examples 1 to 4 is better than that of the rubber mixture of comparative example 1, which shows that the performance is cracked when white carbon black is directly used as a filler, and the performance is effectively improved by adding the white carbon black with the surface grafted with maleimide.
The rubber compound obtained in the examples and the comparative examples is subjected to a durability test, specifically, the rubber compound obtained is used as a rubber damper to be subjected to a fatigue test with the following parameters: cycle endurance tests were performed in a shock disc, one cycle test: preloading 1200N, loading to 1600N, testing for 1min at the frequency of 3Hz, and stopping unloading for 15S; the endurance cycle was 6000 times or more, and whether cracking or abrasion occurred was observed, and the results are shown in the following table 2:
TABLE 1 results of endurance tests of the mixes obtained in the examples and comparative examples
Referring to the above table, the high hardness, wear resistant and durable hydrogenated nitrile rubber material of the present invention has good properties of hardness, breaking strength, wear resistance, rebound and oil resistance, especially has excellent high hardness rebound, wear resistance and durability, and is a preferred material in the novel damping disc of the shaft coupling.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. The high-hardness wear-resistant durable hydrogenated nitrile rubber compound is characterized by comprising the following raw materials in parts by weight:
80-100 parts of hydrogenated nitrile rubber, 4-7 parts of zinc oxide, 0.5-2 parts of stearic acid, 30-60 parts of carbon black, 0-15 parts of white carbon black, 0-20 parts of filler, 1-3 parts of aniline anti-aging agent, 0-15 parts of processing aid and 3-6 parts of peroxide vulcanizing agent;
the white carbon black is the white carbon black with the surface grafted with maleimide.
2. A high hardness abrasion resistant and durable hydrogenated nitrile rubber compound according to claim 1, wherein said hydrogenated nitrile rubber has an acrylonitrile content of 25% or more, a mooney viscosity ML1+4 at 100 ℃ of 50 to 90, and an iodine value of 10 to 35mg/100mg.
3. The high hardness abrasion resistant and durable hydrogenated nitrile rubber compound according to claim 1 or 2, wherein said carbon black is at least one of carbon black N330, carbon black N375 or carbon black N339.
4. The high hardness abrasion resistant and durable hydrogenated nitrile rubber compound according to any one of claims 1 to 3, wherein the white carbon black with the maleimide grafted on the surface is obtained by reacting white carbon black and N- (2-hydroxyethyl) maleimide with dibutyltin dilaurate as a catalyst for 3 to 5 hours after heating to 50 to 70 ℃;
preferably, the mass ratio of the white carbon black to the N- (2-hydroxyethyl) maleimide is 10-15.
5. The high hardness abrasion resistant and durable hydrogenated nitrile rubber compound according to any one of claims 1 to 4, wherein said filler is a silicate;
preferably, the silicate is at least one of magnesium aluminum hydrotalcite or calcined kaolin.
6. A high hardness abrasion resistant and durable hydrogenated nitrile rubber compound according to any of claims 1 to 5, wherein said aniline antioxidant is at least one of 4,4' -bis (phenylisopropyl) diphenylamine, N-isopropyl-N ' -phenyl-p-phenylenediamine or N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine.
7. The high durometer abrasion resistant and durable hydrogenated nitrile rubber compound according to any of the claims 1 to 6, wherein the processing aid comprises saturated fatty acid esters and/or erucamide.
8. A high hardness, abrasion resistant and durable hydrogenated nitrile rubber compound according to any of claims 1 to 7, wherein said peroxide curing agent is at least one of 1, 4-di-tert-butylperoxycumene, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, dicumyl peroxide or 1, 3-bis (2-tert-butylperoxyisopropyl) benzene.
9. A process for the preparation of a high hardness abrasion resistant and durable hydrogenated nitrile rubber compound according to any one of claims 1 to 8, comprising: adding hydrogenated nitrile rubber, zinc oxide, stearic acid, carbon black, white carbon black, a filler, an aniline anti-aging agent and a processing aid into an internal mixer, mixing uniformly, adding a peroxide vulcanizing agent, mixing uniformly, and finally vulcanizing to obtain a finished product, namely the high-hardness wear-resistant durable hydrogenated nitrile rubber compound.
10. The method for preparing a high hardness abrasion resistant and durable hydrogenated nitrile rubber compound according to claim 9, wherein the vulcanization temperature is 155-165 ℃ and the vulcanization time is 20-60min.
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| JPS6429385A (en) * | 1987-07-27 | 1989-01-31 | Bridgestone Corp | Silane coupling agent |
| KR20010046857A (en) * | 1999-11-16 | 2001-06-15 | 조충환 | A rubber composition containing maleimide coupling agent |
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